Density functional theories of surface interactions in salt solutions
(2009) In Journal of Chemical Physics 130(6).- Abstract
- Most current density functional theories rely upon the presence of hard cores, also between ions of like charge. These hard cores should in principle reflect exchange repulsion. However, by the way in which these theories are formulated, the hard cores effectively determine the range of ion-ion correlations. This is because the mutual repulsion between like-charged ions is truncated below the corresponding hard sphere diameter. In most relevant applications, at least those related to ion correlations and surface forces in colloidal dispersions, exchange repulsion between like-charged ions is unimportant. This can easily be demonstrated by simulations. Unfortunately, the hard cores can in practice serve as fitting parameters in calculations... (More)
- Most current density functional theories rely upon the presence of hard cores, also between ions of like charge. These hard cores should in principle reflect exchange repulsion. However, by the way in which these theories are formulated, the hard cores effectively determine the range of ion-ion correlations. This is because the mutual repulsion between like-charged ions is truncated below the corresponding hard sphere diameter. In most relevant applications, at least those related to ion correlations and surface forces in colloidal dispersions, exchange repulsion between like-charged ions is unimportant. This can easily be demonstrated by simulations. Unfortunately, the hard cores can in practice serve as fitting parameters in calculations with traditional density functional theory. In this work, we present alternative density functional theories to describe aqueous salt solutions. In these approaches, an approximation of the relevant "Coulomb hole" that results from correlations between like-charged ions is calculated for the system under study. Hence, our theories are completely free from fitting parameters, and the results are appropriately insensitive to the exchange repulsion acting between ions of like charge. The theories are evaluated by comparing predictions with simulation data, with an emphasis on ion correlations and surface interactions. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/1372163
- author
- Forsman, Jan LU
- organization
- publishing date
- 2009
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- statistical mechanics, liquid theory, density functional theory, adsorption, colloids
- in
- Journal of Chemical Physics
- volume
- 130
- issue
- 6
- publisher
- American Institute of Physics (AIP)
- external identifiers
-
- wos:000263408800037
- pmid:19222292
- scopus:60349087007
- ISSN
- 0021-9606
- DOI
- 10.1063/1.3071195
- language
- English
- LU publication?
- yes
- additional info
- The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
- id
- d128af45-03d5-4142-8a38-d1cff6535311 (old id 1372163)
- date added to LUP
- 2016-04-01 12:04:54
- date last changed
- 2023-01-03 03:35:47
@article{d128af45-03d5-4142-8a38-d1cff6535311,
abstract = {{Most current density functional theories rely upon the presence of hard cores, also between ions of like charge. These hard cores should in principle reflect exchange repulsion. However, by the way in which these theories are formulated, the hard cores effectively determine the range of ion-ion correlations. This is because the mutual repulsion between like-charged ions is truncated below the corresponding hard sphere diameter. In most relevant applications, at least those related to ion correlations and surface forces in colloidal dispersions, exchange repulsion between like-charged ions is unimportant. This can easily be demonstrated by simulations. Unfortunately, the hard cores can in practice serve as fitting parameters in calculations with traditional density functional theory. In this work, we present alternative density functional theories to describe aqueous salt solutions. In these approaches, an approximation of the relevant "Coulomb hole" that results from correlations between like-charged ions is calculated for the system under study. Hence, our theories are completely free from fitting parameters, and the results are appropriately insensitive to the exchange repulsion acting between ions of like charge. The theories are evaluated by comparing predictions with simulation data, with an emphasis on ion correlations and surface interactions.}},
author = {{Forsman, Jan}},
issn = {{0021-9606}},
keywords = {{statistical mechanics; liquid theory; density functional theory; adsorption; colloids}},
language = {{eng}},
number = {{6}},
publisher = {{American Institute of Physics (AIP)}},
series = {{Journal of Chemical Physics}},
title = {{Density functional theories of surface interactions in salt solutions}},
url = {{http://dx.doi.org/10.1063/1.3071195}},
doi = {{10.1063/1.3071195}},
volume = {{130}},
year = {{2009}},
}